TW506983B - Surface treated boron nitride for forming a low viscosity high thermal conductivity polymer based boron nitride composition and method - Google Patents

Abstract

A low viscosity high thermal conductivity polymer-based boron nitride composition and a surface- treated boron nitride material for use as a filler in this composition, and methods of preparation is described. A method for forming a low viscosity high thermal conductivity polymer composite containing particles of hexagonal boron nitride comprising the steps of: (a) treating the surface of the hexagonal boron nitride particles with 1,4-phenylene diisocyanate, (b) thereafter reacting the thus-treated boron nitride particles with a compound of the formula H2N-X-Y, where X is a phenylene, Y is ortho-, meta-, or para-hydroxyl, amino, methyleneamino, ethyleneamino, amido, thiol, epoxy, vinyl, acetylenyl, silanol, nitrile, carboxyl, methacryl, acryl, allyl, anhydride, cyanate, norbornenyl, or maleimido and, where applicable, may have additional substituents selected from the group consisting of -CF3, -CF2CF3, and, -CF2CF2CF3, and (c) combining the surface treated hexagonal boron nitride particles with a monomer selected from the group consisting of benzoxazine, epoxy resins and novoiac or resol phenolic resins and polymerizing the monomer filled with treated boron nitride to form said low viscosity high thermal conductivity polymer composite.

Description

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 —______ B7 Description of Invention (^ — '～-一一 — Worry ^ Field: This issue is specifically about a boron nitride group that forms a low viscosity, high thermal conductivity polymer Compound method, and a surface-treated boron nitride material as a filler to form a boron nitride-based composite compound of the low-viscosity, high-thermal-conductivity biopolymer. Bright background: ― face molding & In the electronics industry, molding compositions help to encapsulate electronic components such as integrated circuit devices, so as to protect edge electronic 7L parts from electrical or environmental damage. Some of the basics of current electronic packaging materials are Features 'includes low thermal expansion coefficient, high thermal conductivity, low dielectric constant, low water absorption, and low viscosity. If the thermal conductivity of the material composition is too low, the coating itself may be detrimental to the covered electronic components' because The coating may hinder the transfer of heat and cause the temperature of the electronic component to rise above the temperature reliability specification of the electronic component. Therefore, it can shrink the & Effective life, especially semiconductor components. The issue of heat dissipation in microelectronics is becoming increasingly important as the demand for denser and faster circuits increases. Polymers with high thermal conductivity are important for applications such as computer cases, battery cases, The packaging of electronic control devices and other products that are difficult to remove is an important consideration. The applicant's parent patent application serial number 08 / 846,457 discloses / a kind of low thermal expansion, high resistance and high thermal conductivity. Polymer composite material. The preferred polymer is a polybenzoxotropic compound filled with boron nitride-containing particles. Based on the filling concentration of the boron nitride filler, thermal conductivity has been demonstrated. ≪ — __ Page 2 Paper size applies Chinese National Standard (CNS) a4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

506983 V. Description of the invention (冋 to 37.5W / mK. Generally, the higher the concentration of boron nitride, the higher the thermal conductivity of the polymer composite (polymer composite). However, the viscosity of this composite also increases with The increase in filler concentration increases proportionally. Beyond the filling τ of a certain filling J, the increased viscosity will cause material handling problems. The mold compound must have appropriate fluidity to enable it to be processed into products. Although additives and / or can be added Modifiers to improve the flow characteristics of the mold compound, but greatly increase the cost and may affect other characteristics, such as strength. Invention: According to the present invention, it is known that hexagonal boron nitride is surface-treated on its f, and 彖 sides after surface treatment. Functional primary and secondary amine bridges are formed. Tiansu is selected from polybenzoxazine, epoxy resin and phenolic resin or soluble I compound known as soluble phenolic tree. A polymer composite that has a large decrease in viscosity regardless of the filling concentration of boron nitride. In other words, a nozzle composition containing boron nitride particles with sufficient filling k degrees and surface treatment according to the present invention has its viscosity The ground is lower than the comparative polymer composite containing untreated boron nitride filler particles. In addition, the thermal conductivity of the polymer composite is related to the filling concentration of the boron nitride filler, but is related to the surface treatment of the boron nitride particles. Irrelevant. The method of the present invention includes the following steps: treatment with phenyl 4-diisocyanate /, angular nitridation of particles; reaction of the treated particles with aminophenols; Among oxygen resins and phenolic resins or soluble phenol resins, an unreacted monomer is selected to be connected with the treated hexagonal nitriding particles to form a composite and polymerize the composite. 506983 A7 B7 V. Description of the invention (The present invention also relates to a surface-treated boron nitride material as a filler for forming a compound compound with a low viscosity and high thermal conductivity polymer. Such surface-treated boron nitride particles have the following molecular formula: BNHCNH- (〇) -hnI m-

b2ncnh ο

NHCNH

'OH (Please read the notes on the back before filling out this page},---1.1— I · I i. · Illustrations are briefly explained: When reading the accompanying illustrations, the advantages of the present invention can be detailed by the following invention It becomes apparent from the description, in which: Figure 1 shows the composition of the polybenzoxazine monomer filled with 30% by weight of boron nitride at 100 GC and the same composition but with untreated nitriding Comparison of the viscosity correlation curve of the two filled with boron. Detailed description of the invention: Graphite is composed of hexagonal arrays or net-like layers of carbon atoms. The hexagonal carbon layers are generally flat and oriented. Arranged so that they are approximately parallel and equidistant from each other. These flat, parallel layers of carbon atoms are considered to be basal planes' connected or bonded together in groups arranged in a lattice. Hexagonal boron nitride In terms of morphology and graphite, page 4 This paper is in accordance with China National Standard (CNS) 8-4 specifications (210X297 mm)-Ordered by the Ministry of Economic Affairs, Intellectual Property Bureau, Employee Consumer Cooperative, printed 506983, invention description (similar to 'all have similar flat Disc-shaped and smooth bottom surface composed of molecules. However, the surface of the edge surface of the boron nitride platelet has amine and hydroxyl functional groups. According to the present invention, it has been found that hexagonal nitriding can be processed The surface chemistry of boron particles modifies the interfacial interaction of these particles so that their functional groups are coupled to the polymer they are filled in. The surface treatment of the nitrided particles consists of two steps, as shown in the reaction scheme summarized below. This treatment In the first step, an isocyanate group, that is, phenyl 1,4-diisocyanate is connected to the amine surface of the edge surface of the particles to form an amine linkage. The second step of the surface treatment is most To continue immediately the first step, to reduce the time of exposure to moisture. In the second step of the treatment, the free isocyanate group preferentially reacts with an amino group of an aminophenol, namely, the amino group of 4-aminophenol to form Additional amido groups. The reaction of amine groups with isocyanate groups is much faster than that of amine groups with test groups. It must be understood that due to the large number of amine groups available, this surface treatment may also be combined with other Functional group For example, in the second step of the treatment, it is replaced by another aminophenol compound such as the following formula: h2n-x_y where X is a linear or branched aliphatic spacer having one to forty carbon atoms A functional group (spacer group), or a phenylene. The phenylene group may be substituted ortho, meta, or para by the Y functional group. At the same time, it can replace other available hydrogen atoms to improve compatibility ( compatibility) or reactivity with the matrix resin. These functional groups are on page 5. The paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

、 1T ·· 丨 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 506983 A7 --B7 V. Description of the invention () Including methyl, ethyl, propyl, hydroxyl, nitro, methoxy, and ethoxy , Phenyl or other gamma functional groups. Occasionally, boron nitride surface treatment may be a good choice to reduce the water content at the filler / matrix interface. Using F or CF3 as a substituent to replace other available hydrogen atoms may help reduce the reactivity with the matrix resin. Y is a functional group which is preset to have a chemical reaction or strong physical effect with the matrix resin. In addition to hydroxyl groups, these functional groups include amino groups, methyleamino groups, ethyleneamin groups, amido groups, thiol groups, epoxy groups, ethenyl groups, and acetylene groups. Base, silanol, nitrile group, carboxyl group, methacryl group, propenyl group, glycyl group, hepatic group, Dai & 1 hydrazone, a fused ring [2,2,1] heptyl- [5] group (norbornenyl), and maleimido (maleimid), but not limited thereto. These functional groups may also contain -CF3, -CF2CF3, -CF2CF2CF3 or other fluorinated compounds. When hydrophobicity is added to the surface of the filler, the reaction with the matrix resin is reduced. --------------------- Order --------- line (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperatives, page 6. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 506983 A7 B7. 5. Description of the invention () The general reaction process of the invention is summarized as follows

NCO- (㈠V OCN

Let Η2Ν-Χ ~ γ

Where X and Y are as defined above. -------- I——0 -------- Order --------- ΜΨ (Please read the notes on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives, page 7. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 506983 A7 _B7_ V. Description of the invention () A preferred embodiment of the present invention, in the second step, An ortho, para or meta substituted aminophenol is used as one of the reactants, namely:

NC〇- < (>-OCN

-BNHCNH— (〇V 〇CN

II Ό

NCNH- < (> ~ 〇CN +

OH

-BNHCNH

(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

OH page 8 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) N Description of invention (further specific embodiment, in the second step, it is divided into 4-amino groups (please first Read the note on the back? Matters need to fill in this page)

h2n-^)-OH as one of the reactants, the molecular formula of the obtained substance is

The surface treatment of the boron nitride particles uses tetrahydrofuran as a preferred solvent. The following is a detailed example of a surface treatment procedure: Hexagonal gasification filler particles ("Polarje 180") Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (polartherml80) is an advanced pottery from Cleveland, Ohio Supply from the capital company. The ceramic particles have a medium size of 6.8 microns, a surface area of 6.6 square meters per gram, and a soluble pendant acid salt content of about 0.2%. Clean boron nitride particles before use to remove residual surface contaminants that may be left over from powder processing. For the cleaning of boron nitride particles, it is best to use a 2% solution of ice-cooled acid in deionized water. The aqueous acetic acid / nitriding shed slurries may consist of 7% solids by weight, stir at 85 ° C for four hours, and then use the Buchner funnel and Whatman. GF / B filter paper for suction filtration. Page 9 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China and later, the invention description (<, twice the volume of fresh deionized water used in the original water-soluble acetic acid washing solution can be used to clean the boron nitride particles again. ), The boron nitride filter cake can be carefully divided into chunks and dried in a not: air circulation oven. After an hour, the small pieces of boron nitride are further divided into more similar The state of the powder was put into the oven overnight. The powder recovery rate was 9 § · 10/0 during the cleaning process. Due to the increase in powder filler, the cleaning process also caused a substantial reduction in volume of about 50%. Boron nitride particles were added to a three-necked reaction flask. According to a solid slurry ratio of 8% by weight, the nitriding shed and τ η F were added. At cheese λ, about 1/3 of the total amount of THF was added to the flask. Then magnetically stirred Stir the boron nitride / THF slurry and cover it with argon. At the same time, add phenyl 4-diisocyanate to additional THF, stir and warm. 丨, 4 • phenyl diisocyanate The amount is 0.3% by weight of the total After that, the 1,4-diisocyanate phenyl vinegar solution was slowly added to the stirring boron nitride slurry. After the remaining THF to be added to the slurry was added to the reaction flask, the reaction flask was moved to an oil bath and heated And refluxed for four hours. 4-aminophenol solution on the surface of THF was prepared according to the total solution concentration of 0.6% by weight. Then treated with 1,4-diisocyanate and suction filtered, the obtained nitriding solution was removed. The cake was re-dispersed in fresh THF, and the boron nitride slurry was slowly added to the 4-aminophenol solution. The boil nitride slurry was heated and stirred for two hours, and then filtered with suction. Fresh THF was added to the boron nitride. , And suction filtration. Move the chaotic boron cake, re-disperse in fresh THF, stir: stir, and then suction filter again. Move the boron nitride cake, carefully divided into pages 10 This paper is for China National Standard (CNS) A4 Specification (210 X 297 mm) --------------------- Order --------- (Please read the back first Note to note? Please fill in this page again.) A7 V. Description of the invention (small piece, dry overnight in a fume hood. Are these two purified? Angled boron nitride particles. In addition to the hydroxyl groups, the surface functional groups also have first-order and second-order amine groups. According to the present invention, it has been proven to be selected from the group consisting of benzopyrene, household gas resin and phenolic resin or soluble phenolic resin. Furen & set resin system and filler containing boron nitride particles ^ Compared with similar filled resin systems using surface-treated hexagonal nitrides, Viscosity is greatly reduced. It is clearly shown in Figure 1 that, at 100 ° C, compared with the untreated nitrided filling system, the weight percent " 30% boron nitride filled BA ® Benzene chew Lacquer monomer, viscosity reduced by 59%. The use of pressure and / or ... to polymerize fluorene monomers into polybenzoxazines is well known to those skilled in the art. Bureau of Intellectual Property, Ministry of Economic Affairs (please read the notes on the back before filling this page) In the parent application serial number 08/846457, teach a composition containing a benzoxazine resin and a filler material, the filler includes boron nitride The particles, in order to increase the thermal conductivity to 37.5 W / mK < higher, may allow the weight percentage of boron nitride to be filled above 60%, and the upper limit is a concentration standard of 90% by weight. The advantage of using surface-treated hexagonal boron nitride particles as a filler material is to allow the compound to have a higher filling concentration. Compared with the same compound that uses untreated particles and has a higher filling amount, the viscosity does not increase, thereby Provide enhanced thermal conductivity and lower viscosity or simply reduce the viscosity of the filled polymeric composite to enhance its processability. Printed by the Consumer News Agency. Page 11 This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

506983 90.11. I 9 Hu]] Li Lidu No. Wei fj case% year " Month Amendment VI. Patent application scope 1 · A method for forming a polymer with low viscosity and high thermal conductivity and containing hexagonal boron nitride particles, It includes the following steps: (a) treating the surface of the hexagonal nitrided particles with 1,4-diisocyanate; (b) thereafter, treating the compound of molecular formula H2N-XY with boron nitride treated as described above Particle reaction, where X is phenylene, Y is ortho, meta or para-chloro, amine, methyleneamino, ethyleneamine, amido, thiol, epoxy, Vinyl, ethynyl, silanol, nitrile, carboxyl, methacryl, propenyl, allyl, anhydride, cyanate, difused ring [2,2,1] ] (Norbornenyl), or maleimido, and, where appropriate, may have additional substituents selected from -cf3, _CF2CF3, -CF2CF2CF3, and (c) from polymer Select a monomer and surface-treated hexagonal boron nitride particles from benzopyrene 51 Qin, epoxy resin, acid resin or drop-type resin. Sub-bonds and polymerizes the filled boron nitride monomer to form the low-viscosity, high-thermal-conductivity polymer compound. 2. The method according to item 1 of the scope of patent application, wherein in the compound having the molecular formula H2N-X-Y, X is a phenylene group, and Y is an -OH group in the ortho, meta, or para position. 3. The method as described in item 1 of the scope of patent application, wherein steps (a) and (b) of the 12th paper size are applicable to China National Standard (CNS) A4 specifications (210 X 297 public love) ----- ---- * --- (Please read the precautions on the back before filling out this page) --- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 506983 8 8 8 8 AB CD Six The Intellectual Property Bureau of the Ministry of Economic Affairs printed a patent application for processing by the Consumer Cooperative, which uses tetrahydrofuran (THF) as a solvent. 5. The surface-treated boron nitride material as described in item 4 of the scope of the patent application, which can be polymerized with any one selected from the group consisting of polybenzoxazine, epoxy resin, and aldehyde resin or soluble phenol resin.物 连接。 Object coupling. 6. A compound for forming a low-viscosity, high-thermal-conductivity polymer composite, which includes a polymer selected from the group consisting of polybenzopyrene 4, an epoxy resin, and a resin or a soluble phenol resin, and a Filler material containing surface-treated boron nitride particles. The surface treatment of the surface-treated boron nitride is shown in the following figure:, page 13 This paper size applies to China National Standard (CNS) A4 (210X 297) Li) (Please read the notes on the back before filling this page) Order- 506983 A8 B8 C8 D8, patent application scope Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where X is a phenylene group, and Y is an ortho, meta or para hydroxyl, amine, methyleneamine, ethyleneamine, amidine, Thiol, epoxy, ethynyl, ethynyl, silanol, nitrile, carboxyl, methylpropionyl, propionyl, allyl, anhydride, cyanate, difused ring [ 2,2,1] heptazone- [5] group (norbornenyl), or maleimido, and, where appropriate, may have a member selected from -CF3, -CF2CF3, and -CF2CF2CF3 Substitute for the amount of Ebu. 7 · The compound as defined in item 6 of the scope of the patent application, wherein X is a phenylene group and Y is an -OH group which is ortho, meta, or para. 8. The compound as described in claim 7 of the scope of patent application, wherein X is a phenylene group and Y is a -OH group in the para position. Page η This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) Order -------